EP0616883B1 - Electriacally conductive glass pane obtained by pyrolysis of powder compounds for use as a windscreen for a vehicle - Google Patents
Electriacally conductive glass pane obtained by pyrolysis of powder compounds for use as a windscreen for a vehicle Download PDFInfo
- Publication number
- EP0616883B1 EP0616883B1 EP94109000A EP94109000A EP0616883B1 EP 0616883 B1 EP0616883 B1 EP 0616883B1 EP 94109000 A EP94109000 A EP 94109000A EP 94109000 A EP94109000 A EP 94109000A EP 0616883 B1 EP0616883 B1 EP 0616883B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- glass
- glazing
- layer
- ito
- sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Revoked
Links
- 239000011521 glass Substances 0.000 title claims abstract description 63
- 150000001875 compounds Chemical class 0.000 title abstract description 7
- 239000000843 powder Substances 0.000 title abstract description 5
- 238000000197 pyrolysis Methods 0.000 title abstract description 5
- 230000005540 biological transmission Effects 0.000 claims abstract description 28
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004040 coloring Methods 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005361 soda-lime glass Substances 0.000 claims description 3
- 238000007496 glass forming Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 5
- 229920002457 flexible plastic Polymers 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 65
- 239000004814 polyurethane Substances 0.000 description 12
- 229920002635 polyurethane Polymers 0.000 description 11
- 239000011888 foil Substances 0.000 description 10
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 10
- 210000003298 dental enamel Anatomy 0.000 description 8
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000004800 polyvinyl chloride Substances 0.000 description 7
- 229920000915 polyvinyl chloride Polymers 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- SBFKENUEAOCRNR-UHFFFAOYSA-K indium(3+);triformate Chemical compound [In+3].[O-]C=O.[O-]C=O.[O-]C=O SBFKENUEAOCRNR-UHFFFAOYSA-K 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 238000009434 installation Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 101100536354 Drosophila melanogaster tant gene Proteins 0.000 description 1
- 208000034693 Laceration Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004534 enameling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical group [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer
- Y10T428/31601—Quartz or glass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31627—Next to aldehyde or ketone condensation product
- Y10T428/3163—Next to acetal of polymerized unsaturated alcohol [e.g., formal butyral, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31645—Next to addition polymer from unsaturated monomers
- Y10T428/31649—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31688—Next to aldehyde or ketone condensation product
Definitions
- the present invention relates to a glazing unit provided with an electroconductive coating based on metal oxides obtained by pyrolysis of powdered compounds, usable in particular as a windshield for an automobile.
- the invention relates to a glazing unit comprising such a coating which has a sufficiently low electrical resistance and nevertheless good light transmission in the visible range so that its use as heating glazing for the automobile can be envisaged.
- patent document EP-A-192 009 proposes glazings coated with a layer of pyrolysed ITO (indium tin oxide) obtained from powdered compounds, of thickness 1900 and 3000 Angstroems, having resistances by square which are 11 and 7.5 ohms respectively and light transmission factors of 83 and 82% respectively.
- ITO indium tin oxide
- the 3000 Angstroems layer is purple red in reflection, which aesthetically, harmony with the colors of car bodies, is unlikely to be accepted.
- these pyrolyzed layers have a slight speckling and a light veil which are not at all annoying for glazing used in the building, but which for automotive glazing can be disputed.
- the standards for automobile windshields require that the haze (percentage of diffuse light) is not greater than 0.5%, which is less than what the eye is able to perceive in normal vision. (2 to 3%) and what is accepted for glazing intended for the building industry.
- this prior patent EP 192 009 proposes the production of laminated glazing with an ITO layer, but to facilitate the reducing heat treatment of ITO, it plans to operate said reducing thermal treatment on the laminated glazing produced, with a burner, the burner having the advantage of rapidly heating the ITO layer for treating it, without having time to heat the structure of the glazing, the ITO layer being therefore arranged on an external face of the glazing, directly in contact with the burner flame.
- Document US 4,655,811 proposes layers of ITO deposited under vacuum having resistances per square down to 5 ohms and retaining a light transmission compatible with uses in the automotive field.
- the production costs are high, the production times are long and the increase in thicknesses would further increase these costs and these production times on the one hand and reduce the light transmission too much on the other hand.
- Glazers coated with a stack of layers obtained by vacuum techniques are also known, layers among which is an Ag layer surrounded by dielectric layers.
- These glazings have, like the previous ones already mentioned, an electrical resistance greater than 5 ohms and in addition these layers oxidize and degrade easily, in particular with humidity.
- the glass sheets coated with these layers of layers containing a layer Ag require important precautions when laminating in order to form laminated glazing, because the slightest soiling, the slightest dust screams a visible defect.
- the present invention aims to provide glazing coated with an ITO electroconductive diptt, usable as glazing for the automobile and as a vehicle glazing, capable of being electrically heated thanks to the electrical energy available on the vehicle, including the diptt ITO either risistant, or aesthetic (neutral or identical color that of anti-solar glazing for cars currently used and appriciis, without speckles, without veil, ...) and whose production cost is less expensive than that of glazing be empty.
- glazing having at least one glass plate coated with an ITO layer, obtained by pyrolysis of a pulverulent mixture of a tin compound, in particular DBTO (dibutyltin oxide) and a compound of indium, in particular indium formate, then by reducing treatment of the layer thus obtained, associated with a sheet of a material of the flexible plastic material type with an index approaching more that of the ITO layer than the 'air index.
- ITO dibutyltin oxide
- the ITO layer on a face of glass sheet which allows it to be brought into contact with a flexible material capable of intimately marrying any surface irregularities of the ITO layer, thanks to the high index of this material, the speckles are practically eliminated and in addition the possible hazy appearance of the ITO layer is nonexistent and compatible with regulations.
- the ITO layer has a thickness such that its color is a popular color for automobile glazing, in particular a slightly green color in reflection.
- the ITO layer has a thickness of at least 330 nanometers, which gives it a resistance per square equal to or less than 5 Ohms and preferably a thickness of the order of 350-380 nanometers , which gives it a resistance per square of the order of 4.5 Ohms - 4.0 Ohms.
- the ITO layer has a thickness of the order of 180 nanometers, which gives it a resistance per square of the order of 10 Ohms.
- the glass plate carrying the ITO coating and / or another plate glass associated with it to constitute with it a laminated glazing is in tinted glass in its mass, of the type known as "TSA” or "TSA 2+ ".
- FIG. 1 shows a glazing unit consisting of a single glass plate 11 coated with a layer 12 of ITO, and associated with a sheet 13 of a flexible material with a refractive index greater than that of the air comprised between the air index and the index of the ITO layer (1.8) and in particular of the order of 1.5, capable of perfectly adhering to the layer 12, of intimately embracing any irregularities, suitable also to be used as it is, that is to say without protection or covering.
- the PU sheet is a two-layer sheet comprising a layer of energy-absorbing thermoplastic PU and a layer of self-healing and anti-laceration thermosetting PU.
- the plate 11 is made of soda-lime-silica glass conventionally used for automobile and building glazing. It may be a clear glass, that is to say a non-colored glass, having a significant light transmission, greater than 90% under a thickness of 4 mm. It may also be a colored glass in its mass capable of providing increased summer comfort for the passengers of the vehicle or of the room equipped with such glasses, due to its reduced energy transmission factor.
- the coloring of the glass is the same as that of the layer, namely green for the layer thicknesses of the order of 350-380 nm or 180 nm.
- these glasses tinted in their mass by iron oxides have properties of absorption of IR radiation, and therefore in general interesting energy properties, thanks to which summer comfort is increased.
- TSA glass containing Fe 2 O 3 can be used in weight proportions of the order of 0.55 to 0.62%, FeO for approximately 0.11 to 0.16%, this which leads to a Fe 2+ / Fe ratio of the order of 0.19 to 0.25, CoO for less than 12 ppm and even preferably for less than 10 ppm.
- T L high light transmission
- T E relatively low energy transmission factor
- TSA 2+ is colored by the same oxides as above but in slightly different proportions.
- automobile glazing according to the invention can be produced with a glass sheet 11 made of “TSA” glass 3 mm thick, covered with an ITO layer of thickness on the order of 350-380 nm or a fortiori around 180 nm, itself covered with polyurethane as described in the earlier patents already cited.
- the glass thickness "TSA” can be slightly greater, and reach up to 3.5 or 4 mm.
- glazings according to the invention with thicknesses of glass to form the plate 11, less than those set out below, are a fortiori possible since this makes it possible to increase the light transmission and that, consequently, the regulations remain satisfactory.
- FIG. 2 shows a laminated glazing with at least two thicknesses of glass, consisting of a first glass plate 15 coated with a layer 16 of ITO associated with a sheet 17 of a material with a refractive index higher than that of the air, between the air index and the index of the ITO layer (1.8) and in particular of the order of 1.5 able to adhere perfectly to layer 16, to marry it intimately any irregularities, also suitable for constituting the plastic interlayer of laminated glazing, also consisting of a second glass plate 18. If desired, additional sheets of glass, plastic interleaves can be added to form a laminated thicker, more resistant.
- the sheet 17 is for example made of PVB (polyvinyl butyral) conventionally used to produce laminated glazings, PVC (polyvinyl chloride), PU (polyurethane).
- PVB polyvinyl butyral
- PVC polyvinyl chloride
- PU polyurethane
- the glass plate 18 and / or optionally the glass plate 15 is advantageously made of colored glass in its mass, with improved energy properties, as said previously in “TSA” or “TSA 2+ ” glass.
- ITO layers 12 and 16 of the embodiments shown in FIGS. 1 and 2 are obtained by pyrolysis of a mixture of powders of an indium compound as an essential constituent, in particular indium formate (InFo) and a compound tin, especially dibutyltin oxide (DBTO).
- InFo and DBTO the weight proportions are of the order of 90% of InFo and 10% of DBTO; the particle sizes are between 5 and 20 microns and preferably between 5 and 15 microns.
- the distribution of the powder mixture on the glass substrate is carried out using installations already described in detail in the European patent documents published under the numbers 125 513, 130 919, 191 258, 189 709, 188 962.
- FIG. 3 shows the same elements as in FIG. 2 and with the same references, namely, the glass sheet 15, carrying the layer 16 of ITO, a second glass sheet 18 free of any layer, but possibly in a glass colored in its mass, of the type "TSA” or “TSA 2+ ”, the sheet 17 of material of the PVB type, of index greater than that of air and possibly colored, the conductive strips 19a and 19b in particular in the form of foils, arranged substantially horizontally and substantially parallel, one in the upper part of the glazing, the other in the lower part.
- the layer 16 of ITO is deposited on face 3.
- This layer 16 is for example deposited at the outlet of the float bath of a flat glass manufacturing installation, on a ribbon of flat glass manufactured in continued.
- This ribbon is cut into rectangles, then according to the developed shape of the windshield or in general glazing to be produced; this then constitutes the plate 15 coated with its layer 16.
- This plate 15 then receives on its face not coated with ITO, that is to say the face which will constitute the face 4 of the laminated glazing, a deposit 20 of enamel at its periphery by a conventional screen printing technique.
- this plate 15 coated with ITO on one side, with its deposit of peripheral enamel on the other, is associated with another glass plate, plate 18, also cut for example from the ribbon emerging from a float line, in clear glass or in mass-tinted glass.
- This flat plate 18 receives on one of its faces, that which will constitute the face 2 of the laminated glazing, a peripheral deposit of enamel 21.
- this deposit 21 on face 2 is annealed.
- the two glass plates 15 and 18 are paired, that is to say superimposed, face 2 against face 3, and curved simultaneously by heating and for example subsidence on a bending frame or skeleton.
- layer 16 is on a convex face, so it is put in light extension by bending of the glass, without any particular precaution and despite this its properties, in particular electrical properties, are not affected.
- the intermediate sheet 17 of material with an index close to that of the ITO layer, in particular PVB, is cut, associated with the foils 19a and 19b in particular by spot hot welding of said foils on the top and bottom edges of the sheet.
- the metallic foil is not cut, but passes on the other side of the PVB through an incision made in the PVB, then descends vertically along the edge of the PVB until 'at the lower strand 19b of foil.
- the two strands 19b and 19a of tinsel, isolated from one another are associated so as to be able to go out in a single place.
- This sheet of PVB type material is then placed between the two glass plates 15 and 18, the strands 19a and 19b of the foil being attached to the layer 16 on the face 3.
- the ends of the strands 19a and 19b leaving the glazing thus produced are available to be connected to the source of electric current of the vehicle on which the glazing will be mounted.
- these strands 19a and 19b can be cut and connected to a particular connection facilitating the connection with the current source.
- TSA glass plate 18
- the plate 18 can be made of a 2.1 mm or 2.2 mm thick "TSA" glass, the plate 15 coated ITO can be made of a conventional clear glass 2.1 to 2.6 mm thick and the sheet 17 can be a PVB 0.76 mm thick.
- TSA glass
- the plate 15 coated ITO can be made of a conventional clear glass 2.1 to 2.6 mm thick
- the sheet 17 can be a PVB 0.76 mm thick.
- the plate 18 is 2.6 mm thick, all other things being equal the coefficient T L drops slightly below 75% for an ITO layer thickness of the order of 350-380 nm, but satisfies the regulations of countries where a T L of only 70% is required. On the other hand, for an ITO layer thickness of the order of 180 nm, the threshold of 75% is satisfied.
- the current supply strips 19a and 19b are not metallic foils, but screen-printed strips, said screen-printed strips are deposited on the upper and lower edges of the glass plate 15 coated with its ITO layer on this ITO layer, therefore on face 3 of laminated glazing after cutting to the dimensions of the finished glazing and after peripheral enameling on face 4 of the same plate 15.
- these screen-printed bands on the plate 15 are annealed.
- the glazing produced is of the type shown in FIG. 1, that is to say with a single glass plate 11 coated ITO in association with a sheet of material of index higher than that of air and as close as possible to that of ITO, for example PU, the conductive strips 14a and 14b are also either screen printed or foil. They are then in contact with the ITO layer.
- the metal foils or the screen-printed strips are masked by a frame of thermoplastic material mounted in situ by the technique known as encapsulation.
- This encapsulation frame can also serve as a cover, protection and insulation for the strand of metallic foil traveling up to its exit from the glazing on the other side of the PU sheet, that is to say not in contact with the ITO layer.
- the good properties of the ITO layer allow its association with mass-tinted glasses.
- the result is glazing with interesting electrical, optical and thermal properties.
- Thicknesses of glass plates have been proposed previously, by virtue of which the regulations are respected, but, of course, thinner thicknesses than those proposed are a fortiori acceptable, the coefficient T L will only be higher.
- this layer allows the bending of its support after deposition, without special precautions even when after bending said layer is arranged on the convex face of its support.
- This filtering can be used as a heated windshield for cars.
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Abstract
Description
La présente invention concerne un vitrage muni d'un revêtement électroconducteur à base d'oxydes métalliques obtenu par pyrolyse de composés en poudre, utilisable notamment en tant que pare-brise pour automobile.The present invention relates to a glazing unit provided with an electroconductive coating based on metal oxides obtained by pyrolysis of powdered compounds, usable in particular as a windshield for an automobile.
En particulier, l'invention concerne un vitrage comprenant un tel revêtement qui présente une résistance électrique suffisamment basse et malgré tout une bonne transmission lumineuse dans le visible pour que son utilisation en tant que vitrage chauffant pour l'automobile puisse être envisagée.In particular, the invention relates to a glazing unit comprising such a coating which has a sufficiently low electrical resistance and nevertheless good light transmission in the visible range so that its use as heating glazing for the automobile can be envisaged.
Il est connu par divers brevets antérieurs de fabriquer des vitrages revêtus de couches conductrices ayant la transmission lumineuse supérieure à 75 % ou 70 % selon les législations, qui autorise leur utilisation en tant que vitrages pour l'automobile et présentant une résistance par carré de l'ordre de 10 ohms et même descendant jusque 5 ohms.It is known from various prior patents to manufacture glazings coated with conductive layers having light transmission greater than 75% or 70% depending on the legislation, which authorizes their use as glazing for the automobile and having a resistance per square of l '' order of 10 ohms and even down to 5 ohms.
Ainsi le document de brevet EP-A-192 009 propose des vitrages revêtus d'une couche d'ITO (indium tin oxide) pyrolysée obtenue à partir de composés en poudre, d'épaisseur de 1900 et de 3000 Angstroems, présentant des résistances par carré qui sont respectivement de 11 et de 7,5 ohms et des facteurs de transmission lumineuse respectivement de 83 et 82 %.Thus, patent document EP-A-192 009 proposes glazings coated with a layer of pyrolysed ITO (indium tin oxide) obtained from powdered compounds, of thickness 1900 and 3000 Angstroems, having resistances by square which are 11 and 7.5 ohms respectively and light transmission factors of 83 and 82% respectively.
La couche de 3000 Angstroems d'épaisseur est rouge mauve en réflexion, ce qui sur le plan esthétique, harmonie avec les couleurs de carrosseries des voitures, a peu de chance d'être accepté.The 3000 Angstroems layer is purple red in reflection, which aesthetically, harmony with the colors of car bodies, is unlikely to be accepted.
En outre ces couches pyrolysées présentent un léger mouchetis et un léger voile qui ne sont pas du tout génants pour un vitrage utilisé dans le bâtiment, mais qui pour un vitrage automobile peuvent être contestés. Ainsi, les normes pour les pare-brise d'automobiles requièrent que le voile (pourcentage de lumière diffuse) ne soit pas supérieur à 0,5 %, ce qui est inférieur à ce que l'oeil est capable d'apercevoir en vision normale (2 à 3 %) et à ce qui est accepté pour des vitrages destinés au bâtiment.In addition, these pyrolyzed layers have a slight speckling and a light veil which are not at all annoying for glazing used in the building, but which for automotive glazing can be disputed. Thus, the standards for automobile windshields require that the haze (percentage of diffuse light) is not greater than 0.5%, which is less than what the eye is able to perceive in normal vision. (2 to 3%) and what is accepted for glazing intended for the building industry.
Il est à noter que ce brevet antérieur EP 192 009 propose la réalisation de vitrages feuilletés à couche ITO, mais pour faciliter le traitement thermique réducteur de l'ITO, il prévoit d'opérer ledit traitement thermique réducteur sur le vitrage feuilleté réalisé, avec un brûleur, le brûleur ayant l'avantage d'échauffer rapidement la couche d'ITO pour la traiter, sans avoir le temps d'échauffer la structure du vitrage, la couche d'ITO étant pour cela disposée sur une face extérieure du vitrage, directement au contact de la flamme du brûleur.It should be noted that this prior patent EP 192 009 proposes the production of laminated glazing with an ITO layer, but to facilitate the reducing heat treatment of ITO, it plans to operate said reducing thermal treatment on the laminated glazing produced, with a burner, the burner having the advantage of rapidly heating the ITO layer for treating it, without having time to heat the structure of the glazing, the ITO layer being therefore arranged on an external face of the glazing, directly in contact with the burner flame.
Le document de brevet US 4 490 227 propose quant à lui des vitrages revêtus d'une couche d'ITO obtenue par des techniques sous vide, d'épaisseur de l'ordre de 2800 Angstroems, de transmission de l'ordre de 78 %, de résistance au carré approximativement de 7 à 10 ohms.The patent document US Pat. No. 4,490,227 proposes glazings coated with a layer of ITO obtained by vacuum techniques, with a thickness of the order of 2800 Angstroms, of transmission of the order of 78%, resistance square approximately 7-10 ohms.
Ces couches sous vide sont longues à fabriquer, coûteuses et l'obtention de résistances plus faibles augmenterait le temps de fabrication et le coût d'une part, risquerait de faire franchir les 75 % ou 70 % de transmission requis pour des vitrages automobiles d'autre part.These vacuum layers are long to manufacture, expensive and obtaining lower resistances would increase the manufacturing time and the cost on the one hand, would risk crossing the 75% or 70% of transmission required for automotive glazing. somewhere else.
Le document US 4 655 811, propose des couches d'ITO déposées sous vide ayant des résistances par carré descendant jusqu'à 5 ohms et conservant une transmission lumineuse compatible avec les utilisations dans le domaine de l'automobile. Les coûts de production sont élevés, les temps de production sont longs et l'augmentation des épaisseurs augmenterait encore ces coûts et ces temps de production d'une part et diminuerait trop la transmission lumineuse d'autre part.Document US 4,655,811 proposes layers of ITO deposited under vacuum having resistances per square down to 5 ohms and retaining a light transmission compatible with uses in the automotive field. The production costs are high, the production times are long and the increase in thicknesses would further increase these costs and these production times on the one hand and reduce the light transmission too much on the other hand.
Sont également connus des vitrages revêtus d'un empilement de couches obtenues par des techniques sous vide, couches parmi lesquelles est présente une couche d'Ag entourée de couches de diélectriques. Ces vitrages ont, comme les précédents déjà mentionnés, une résistance électrique supérieure à 5 ohms et en outre ces couches s'oxydent et se dégradent facilement, notamment à l'humidité. Par ailleurs, les feuilles de verre revêtues de ces empilements de couches contenant une couche d'Ag, nicessitent des pricautions importantes lors de leur feuilletage en vue de constituer des vitrages feuilletis, car la moindre salissure, la moindre poussihre crie un difaut visible.Glazers coated with a stack of layers obtained by vacuum techniques are also known, layers among which is an Ag layer surrounded by dielectric layers. These glazings have, like the previous ones already mentioned, an electrical resistance greater than 5 ohms and in addition these layers oxidize and degrade easily, in particular with humidity. Furthermore, the glass sheets coated with these layers of layers containing a layer Ag, require important precautions when laminating in order to form laminated glazing, because the slightest soiling, the slightest dust screams a visible defect.
La prisente invention vise fournir un vitrage revjtu d'un diptt ilectroconducteur d'ITO, utilisable en tant que vitrage pour l'automobile et en giniral pour vihicule, susceptible d'jtre chauffi ilectriquement grbce l'inergie ilectrique disponible sur le vihicule, dont le diptt ITO soit risistant, soit esthitique (couleur neutre ou identique celle des vitrages anti-solaires pour automobiles utilisis et appriciis actuellement, sans mouchetis, sans voile, ...) et dont le co{t de production soit moins ilevi que celui des vitrages produits sois vide.The present invention aims to provide glazing coated with an ITO electroconductive diptt, usable as glazing for the automobile and as a vehicle glazing, capable of being electrically heated thanks to the electrical energy available on the vehicle, including the diptt ITO either risistant, or aesthetic (neutral or identical color that of anti-solar glazing for cars currently used and appriciis, without speckles, without veil, ...) and whose production cost is less expensive than that of glazing be empty.
Cette utilisation des vitrages dans l'automobile implique une transmission lumineuse pour l'illuminant A, (TL), importante, qui selon les riglementations doit jtre au moins de 75 % ou 70 %, suivant les ligislations.This use of glazing in the automobile implies a light transmission for the illuminant A, (T L ), significant, which according to the regulations must be at least 75% or 70%, depending on the regulations.
Elle vise de prifirence un vitrage revjtu d'un diptt ilectroconducteur d'ITO ayant une risistance ilectrique par carri igale ou avantageusement infirieure 5 ohms.It is aimed preferably at glazing coated with an ITO electroconductive diptt having an electrical resistance by carri eal or advantageously less than 5 ohms.
En outre, elle vise aussi de prifirence, un vitrage amiliorant le confort d'iti des passagers du vihicule, donc capable de prisenter malgri la transmission lumineuse importante requise par les riglementations, une transmission inergitique abaissie par rapport un vitrage traditionnel.In addition, it also aims primarily, glazing improving the comfort of ati passengers of the vehicle, therefore able to present despite the important light transmission required by the regulations, an energy transmission lowered compared to traditional glazing.
Elle propose pour cela un vitrage ayant au moins une plaque de verre revêtue d'une couche d'ITO, obtenue par pyrolyse d'un mélange pulvérulent d'un composé d'étain, notamment du DBTO (oxyde de dibutylétain) et d'un composé d'indium, en particulier le formiate d'indium, puis par traitement réducteur de la couche ainsi obtenue, associée avec une feuille d'un matériau du type matière plastique souple à indice s'approchant plus de celui de la couche ITO que l'indice de l'air.It therefore proposes glazing having at least one glass plate coated with an ITO layer, obtained by pyrolysis of a pulverulent mixture of a tin compound, in particular DBTO (dibutyltin oxide) and a compound of indium, in particular indium formate, then by reducing treatment of the layer thus obtained, associated with a sheet of a material of the flexible plastic material type with an index approaching more that of the ITO layer than the 'air index.
Cette feuille est en un matériau appartenant au groupe suivant :
- PVC (butyral de polyvinyle),
- PVC (chlorure de polyvinyle),
- PU (polyuréthane),
- PVC (polyvinyl butyral),
- PVC (polyvinyl chloride),
- PU (polyurethane),
Grâce à la disposition de la couche ITO sur une face de feuille de verre qui permette sa mise en contact avec un matériau souple apte à épouser intimement les éventuelles irrégularités de surface de la couche ITO, grâce à l'indice élevé de ce matériau, les mouchetis sont pratiquement supprimés et en outre le possible aspect voilé de la couche ITO est inexistant et compatible avec les réglementations.Thanks to the arrangement of the ITO layer on a face of glass sheet which allows it to be brought into contact with a flexible material capable of intimately marrying any surface irregularities of the ITO layer, thanks to the high index of this material, the speckles are practically eliminated and in addition the possible hazy appearance of the ITO layer is nonexistent and compatible with regulations.
Avantageusement, la couche ITO a une épaisseur telle que sa couleur est une couleur appréciée pour les vitrages d'automobile, en particulier une couleur légèrement verte en réflexion.Advantageously, the ITO layer has a thickness such that its color is a popular color for automobile glazing, in particular a slightly green color in reflection.
Suivant un premier mode de réalisation, la couche d'ITO a une épaisseur d'au moins 330 nanomètres, ce qui lui confère une résistance par carré égale ou inférieure à 5 Ohms et de préférence une épaisseur de l'ordre de 350-380 nanomètres, ce qui lui confère une résistance par carré de l'ordre de 4,5 Ohms - 4,0 Ohms.According to a first embodiment, the ITO layer has a thickness of at least 330 nanometers, which gives it a resistance per square equal to or less than 5 Ohms and preferably a thickness of the order of 350-380 nanometers , which gives it a resistance per square of the order of 4.5 Ohms - 4.0 Ohms.
Selon un autre mode de réalisation, la couche ITO a une épaisseur de l'ordre de 180 nanomètres, ce qui lui confère une résistance par carré de l'ordre de 10 Ohms.According to another embodiment, the ITO layer has a thickness of the order of 180 nanometers, which gives it a resistance per square of the order of 10 Ohms.
Avantageusement pour conférer au vitrage des propriétés de transmission énergétique améliorée visant à accroître le confort d'été et également pour contribuer à l'amélioration de l'aspect dudit vitrage, la plaque de verre portant le revêtement d'ITO et/ou une autre plaque de verre qui lui est associée pour constituer avec elle un vitrage feuilleté est en verre teinté dans sa masse, du type dit « TSA » ou « TSA2+ ».Advantageously to give the glazing improved energy transmission properties aimed at increasing summer comfort and also to contribute to improving the appearance of said glazing, the glass plate carrying the ITO coating and / or another plate glass associated with it to constitute with it a laminated glazing is in tinted glass in its mass, of the type known as "TSA" or "TSA 2+ ".
L'invention sera maintenant décrite plus en détail en référence aux figures jointes qui représentent :
- figure 1 : une première variante d'un vitrage selon l'invention, en vue éclatée,
- figure 2 : un vitrage feuilleté ayant selon l'invention une couche d'ITO,
- figure 3 : un vitrage feuilleté selon l'invention ayant reçu ses dépôts d'émail et amenées de courant électrique en vue d'être monté en tant que pare-brise d'automobile.
- FIG. 1 : a first variant of a glazing unit according to the invention, in exploded view,
- FIG. 2 : laminated glazing having, according to the invention, an ITO layer,
- Figure 3 : a laminated glazing according to the invention having received its enamel deposits and supplied with electric current in order to be mounted as an automobile windshield.
La figure 1 montre un vitrage constitué d'une seule plaque de verre 11 revêtue d'une couche 12 d'ITO, et associée à une feuille 13 d'un matériau souple à indice de réfraction supérieur à celui de l'air compris entre l'indice de l'air et l'indice de la couche d'ITO (1,8) et notamment de l'ordre de 1,5, apte à parfaitement adhérer sur la couche 12, à en épouser intimement les éventuelles irrégularités, apte également à être utilisée telle quelle, c'est-à-dire sans protection ou recouvrement.FIG. 1 shows a glazing unit consisting of a
Une telle feuille 13, à base de polyuréthane (PU) est décrite en détail dans les documents de brevets publiés en EUROPE sous les numéros 54 491, 132 198, 133 090 et le document de brevet publié en FRANCE sous le numéro 2 398 606. Selon ces brevets, la feuille de PU est une feuille bicouche comprenant une couche de PU thermoplastique absorbeur d'énergie et une couche de PU thermodurcissable autocicatrisante et antilacération.Such a
La plaque 11 est en verre silico-sodo-calcique utilisé classiquement pour les vitrages automobiles et bâtiments. Il peut s'agir d'un verre clair, c'est-à-dire non coloré, présentant une transmission lumineuse importante, supérieure à 90% sous une épaisseur de 4 mm. Il peut s'agir aussi, d'un verre coloré dans sa masse apte à procurer un confort d'été accru pour les passagers du véhciule ou du local équipé de tels verres, du fait de son facteur de transmission énergétique réduit.The
Avantageusement la coloration du verre est la même que celle de la couche, à savoir vert pour les épaisseurs de couche de l'ordre de 350-380 nm ou 180 nm.Advantageously, the coloring of the glass is the same as that of the layer, namely green for the layer thicknesses of the order of 350-380 nm or 180 nm.
Ainsi du seul fait de la coloration du verre, les éventuelles légères irrégularités de couleur de la couche sont masquées. En outre la couleur verte est fortement appréciée pour les vitrages automobiles.Thus, by the sole fact of the coloring of the glass, any slight irregularities in the color of the layer are masked. In addition, the color green is highly appreciated for automotive glazing.
Par ailleurs, ces verres teintés dans leur masse par des oxydes de fer, possèdent des propriétés d'absorption du rayonnement IR, et donc en général des propriétés énergétiques intéressantes, grâce auxquelles le confort d'été est accru.In addition, these glasses tinted in their mass by iron oxides, have properties of absorption of IR radiation, and therefore in general interesting energy properties, thanks to which summer comfort is increased.
Ainsi comme verre coloré, on peut utiliser du verre dit « TSA » contenant Fe2O3 dans des proportions pondérales de l'ordre de 0,55 à 0,62%, FeO pour environ 0,11 à 0,16%, ce qui conduit à un rapport Fe2+/Fe de l'ordre de 0,19 à 0,25, CoO pour moins de 12 ppm et même de préférence pour moins de 10 ppm. Il en résulte des propriétés par exemple pour une épaisseur de 3,85 mm de transmission lumineuse (TL) élevées voisines de 78%, un facteur énergétique de transmission (TE) relativement bas et voisin de 60, ce qui conduit à un rapport TL/TE de l'ordre de 1,30.Thus as colored glass, so-called “TSA” glass containing Fe 2 O 3 can be used in weight proportions of the order of 0.55 to 0.62%, FeO for approximately 0.11 to 0.16%, this which leads to a Fe 2+ / Fe ratio of the order of 0.19 to 0.25, CoO for less than 12 ppm and even preferably for less than 10 ppm. This results in properties for example for a thickness of 3.85 mm of high light transmission (T L ) close to 78%, a relatively low energy transmission factor (T E ) and close to 60, which leads to a ratio T L / T E of the order of 1.30.
On peut aussi utiliser comme verre coloré, en particulier lorsque la réglementation n'impose qu'une transmission lumineuse de 70%, un verre un peu plus coloré que le « TSA », mais présentant par contre une transmission lumineuse un peu plus faible, à savoir un « TSA2+ ».One can also use as colored glass, in particular when the regulation imposes only a light transmission of 70%, a glass a little more colored than "TSA", but having on the other hand a slightly weaker light transmission, with know a "TSA 2+ ".
Ce « TSA2+ » est coloré par les mêmes oxydes que précédemment mais dans des proportions légèrement différentes.This "TSA 2+ " is colored by the same oxides as above but in slightly different proportions.
Ainsi les proportions d'oxydes métalliques sont les suivantes :
- Fe2O3 : approximativement compris entre 0,75 et 0,90%
- FeO: approximativement compris entre 0,15 et 0,22%
- CoO : inférieur à 17 ppm et même de préférence inférieur à 10 ppm soit Fe2+/Fe = 0,20 environ.
- Fe 2 O 3 : approximately between 0.75 and 0.90%
- FeO: approximately between 0.15 and 0.22%
- CoO: less than 17 ppm and even preferably less than 10 ppm, ie Fe 2+ / Fe = approximately 0.20.
Il en résulte pour ce verre « TSA2+ », en 3,85 mm d'épaisseur les propriétés suivantes :
- TL : de l'ordre de 72%
- TE : de l'ordre de 50%
- T L : around 72%
- T E : around 50%
Ainsi un vitrage automobile selon l'invention peut être réalisé avec une feuille de verre 11 en verre « TSA » d'épaisseur 3 mm, recouvert d'une couche ITO d'épaisseur de l'ordre de 350-380 nm ou a fortiori de l'ordre de 180 nm, elle-même recouverte de polyuréthane comme décrit dans les brevets antérieurs déjà cités. Avec l'épaisseur de couche de 180 nm, l'épaisseur de verre « TSA » peut être légèrement plus importante, et atteindre jusqu'à 3,5 ou 4 mm.Thus automobile glazing according to the invention can be produced with a
Il en résulte un vitrage de couleur très légèrement verte en transmission, verte en réflexion ayant une TL compatible avec la réglementation auto (plus de 75%) et une TE de l'ordre de 1,40.The result is a very slightly green glazing in transmission, green in reflection having a T L compatible with car regulations (more than 75%) and a T E of the order of 1.40.
Si l'on veut à la place du verre « TSA » employer du « TSA2+ », en ayant des coefficients de transmission lumineuse compatibles avec les réglementations, on peut choisir une plaque de verre 11 en verre « TSA2+ » de 3 mm d'épaisseur, de préférence avec une épaisseur de couche de 180 nm. Il en résulte alors pour le vitrage fini un coefficient TL supérieur à 70%, un coefficient TL/TE de l'ordre de 1,50, c'est-à-dire une transmission énergétique réduite et donc un confort d'été amélioré.If you want to use "TSA 2+ " instead of "TSA" glass, having light transmission coefficients compatible with regulations, you can choose a
Bien entendu des vitrages selon l'invention avec des épaisseurs de verre pour constituer la plaque 11, inférieures à celles énoncées ci-dessous, sont a fortiori possibles puisque cela permet d'augmenter la transmission lumineuse et qu'en conséquence les réglementations restent satisfaisantes.Of course, glazings according to the invention with thicknesses of glass to form the
La figure 2 montre un vitrage feuilleté à au moins deux épaisseurs de verre, constitué d'une première plaque de verre 15 revêtue d'une couche 16 d'ITO associée à une feuille 17 d'un matériau à indice de réfraction supérieur à celui de l'air, compris entre l'indice de l'air et l'indice de la couche d'ITO (1,8) et notamment de l'ordre de 1,5 apte à parfaitement adhérer sur la couche 16, à en épouser intimement les éventuelles irrégularités, apte également à constituer l'intercalaire plastique d'un vitrage feuilleté, constitué également d'une seconde plaque de verre 18. Si désiré, des feuilles supplémentaires de verre, d'intercalaires plastiques peuvent être ajoutées pour former un feuilleté plus épais, plus résistant.FIG. 2 shows a laminated glazing with at least two thicknesses of glass, consisting of a
La feuille 17 est par exemple en PVB (butyral de polyvinyle) classiquement utilisé pour réaliser des vitrages feuilletés, en PVC (chlorure de polyvinyle), en PU (polyuréthane).The
La plaque de verre 18 et/ou éventuellement la plaque de verre 15 est avantageusement en verre coloré dans sa masse, à propriétés énergétiques améliorées, comme dit précédemment en verre « TSA » ou « TSA2+ ».The
Les couches 12 et 16 d'ITO des réalisations montrées figures 1 et 2 sont obtenues par pyrolyse d'un mélange de poudres d'un composé d'indium comme constituant essentiel, notamment le formiate d'indium (InFo) et d'un composé d'étain, notamment de l'oxyde de dibutylétain (DBTO). Dans le cas de InFo et DBTO les proportions pondérales sont de l'ordre de 90% de InFo et 10% de DBTO ; les granulométries sont comprises entre 5 et 20 microns et de préférence entre 5 et 15 microns.ITO layers 12 and 16 of the embodiments shown in FIGS. 1 and 2 are obtained by pyrolysis of a mixture of powders of an indium compound as an essential constituent, in particular indium formate (InFo) and a compound tin, especially dibutyltin oxide (DBTO). In the case of InFo and DBTO the weight proportions are of the order of 90% of InFo and 10% of DBTO; the particle sizes are between 5 and 20 microns and preferably between 5 and 15 microns.
Un tel mélange de InFo et DBTO est décrit dans le document de brevet européen 192 009.Such a mixture of InFo and DBTO is described in European patent document 192 009.
La distribution du mélange de poudres sur le substrat en verre est faite à l'aide d'installations déjà décrites en détail dans les documents de brevets européens publiés sous les n° 125 513, 130 919, 191 258, 189 709, 188 962.The distribution of the powder mixture on the glass substrate is carried out using installations already described in detail in the European patent documents published under the numbers 125 513, 130 919, 191 258, 189 709, 188 962.
Pour pouvoir alimenter électriquement la couche 12 ou 16 des bandes d'amenée de courant sont à mettre en place.To be able to electrically supply the
Un vitrage du type de celui de la figure 2 est montre en vue éclatée plus détaillée, avec tous ses équipements (bandes conductrices dépôts d'émail) en figure 3. On retrouve sur cette figure 3 les mêmes éléments qu'en figure 2 et avec les mêmes références, à savoir, la feuille de verre 15, portant la couche 16 d'ITO, une seconde feuille de verre 18 exempte de toute couche, mais éventuellement en un verre coloré dans sa masse, du type « TSA » ou « TSA2+ », la feuille 17 de matière du type PVB, d'indice supérieur à celui de l'air et éventuellement colorée, les bandes conductrices 19a et 19b notamment sous la forme de clinquants, disposées sensiblement horizontalement et sensiblement parallèles, l'une en partie haute du vitrage, l'autre en partie basse.Glazing of the type of that of FIG. 2 is shown in a more detailed exploded view, with all of its equipment (conductive strips of enamel deposits) in FIG. 3. This FIG. 3 shows the same elements as in FIG. 2 and with the same references, namely, the
Comme montré sur la figure 3, la couche 16 d'ITO est déposée en face 3. Cette couche 16 est par exemple déposée à la sortie du bain float d'une installation de fabrication de verre plat, sur un ruban de verre plat fabriqué en continu. Ce ruban est découpé en rectangles, puis suivant la forme développée du pare-brise ou en général vitrage à réaliser ; ceci constitue alors la plaque 15 revêtue de sa couche 16. Cette plaque 15 reçoit alors sur sa face non revêtue d'ITO, c'est-à-dire la face qui constituera la face 4 du vitrage feuilleté, un dépôt 20 d'émail à sa périphérie par une technique classique de sérigraphie. Ensuite cette plaque 15 revêtue d'ITO d'un côté, avec son dépôt d'émail périphérique de l'autre, est associée avec une autre plaque de verre, la plaque 18, découpée elle aussi par exemple dans le ruban sortant d'une ligne float, en verre clair ou en verre teinté dans sa masse. Cette plaque 18 plane reçoit sur une de ses faces, celle qui constituera la face 2 du vitrage feuilleté, un dépôt périphérique d'émail 21. Avantageusement, ce dépôt 21 en face 2 est recuit.As shown in FIG. 3, the
Les deux plaques de verre 15 et 18 sont appairées, c'est-à-dire superposées, face 2 contre face 3, et bombées simultanément par chauffage et par exemple affaissement sur un cadre ou squelette de bombage.The two
La plaque 15 seule, ou les deux plaques encore superposées à la suite du bombage, est (sont) alors soumise(s) au traitement réducteur pour valoriser les propriétés de la couche d'ITO 16. Dans les pare-brise de forme bombée classique, la couche 16 est sur une face convexe, elle est donc mise en légère extension par bombage du verre, sans précaution particulière et malgre cela ses propriétés, en particulier électriques ne sont pas affectées.The
La feuille intercalaire 17 de matière à indice voisin de celui de la couche d'ITO, en particulier en PVB, est découpée, associée avec les clinquants 19a et 19b notamment par soudage ponctuel à chaud desdits clinquants sur les bords haut et bas de la feuille. Avantageusement, à une extrémité de la bande haute 19a, le clinquant métallique n'est pas coupé, mais passe de l'autre côté du PVB au travers d'une incision pratiquée dans le PVB, puis descend verticalement le long du bord du PVB jusqu'au niveau du brin inférieur 19b de clinquant. Les deux brins 19b et 19a de clinquant, isolés l'un de l'autre sont associés pour pouvoir sortir en un endroit unique.The
Cette feuille de matière type PVB est alors mise en intercalaire entre les deux plaques de verre 15 et 18, les brins 19a et 19b du clinquant étant accolés à la couche 16 sur la face 3.This sheet of PVB type material is then placed between the two
L'ensemble du vitrage ainsi réalisé est feuilleté par les techniques classiques du feuilletage, par pressage, action du vide et de la chaleur. Cette technique de feuilletage étant classique, elle ne sera pas développée ici. Signalons seulement que des pressions de l'ordre de 10 bars, des températures de l'ordre de 130°C peuvent être mises en oeuvre à cet effet pendant des temps de l'ordre de l'heure.All of the glazing thus produced is laminated by conventional lamination techniques, by pressing, vacuum and heat action. This lamination technique is conventional, it will not be developed here. It should only be noted that pressures of the order of 10 bars, temperatures of the order of 130 ° C. can be used for this purpose for times of the order of an hour.
Les extrémités des brins 19a et 19b sortant du vitrage ainsi réalisé sont disponibles pour être branchés sur la source de courant électrique du véhicule sur lequel le vitrage sera monté.The ends of the
Eventuellement, ces brins 19a et 19b peuvent être coupés et reliés a une connexion particulière facilitant la liaison avec la source de courant.Optionally, these
On peut comme déjà dit utiliser pour la plaque de verre 18 un verre dit "TSA" pour améliorer les qualités énergétiques du vitrage.We can as already said use for the glass plate 18 a glass called "TSA" to improve the energy qualities of the glazing.
Ainsi la plaque 18 peut être en un verre "TSA" de 2,1 mm ou 2,2 mm d'épaisseur, la plaque 15 revêtue ITO peut être en un verre clair classique de 2,1 à 2,6 mm d'épaisseur et la feuille 17 peut être un PVB de 0,76 mm d'épaisseur. Il en résulte un vitrage d'aspect légèrement verdâtre, de couleur parfaitement uniforme avec un coefficient TL de l'ordre de 77 %, donc en accord avec toutes les réglementations en matière de vitrage auto et un coefficient TE de l'ordre de 50 % soit un rapport TL/TE de l'ordre de 1,5.Thus the
Dans un autre mode de réalisation la plaque 18 a 2,6 mm d'épaisseur, toutes autres choses égales par ailleurs le coefficient TL tombe légèrement en dessous de 75 % pour une épaisseur de couche ITO de l'ordre de 350-380 n.m, mais satisfait la réglementation des pays où un TL de seulement 70 % est éxigé. Par contre, pour une épaisseur de couche ITO de l'ordre de 180 n.m, le seuil de 75 % est satisfait.In another embodiment, the
Dans la mesure où les bandes d'amenée de courant 19a et 19b ne sont pas des clinquants métalliques, mais des bandes sérigraphiées, lesdites bandes sérigraphiées sont déposées sur les bords supérieurs et inférieurs de la plaque de verre 15 revêtue de sa couche ITO sur cette couche ITO, donc en face 3 du vitrage feuilleté après découpe aux dimensions du vitrage fini et après émaillage périphérique en face 4 de la même plaque 15.Insofar as the current supply strips 19a and 19b are not metallic foils, but screen-printed strips, said screen-printed strips are deposited on the upper and lower edges of the
Avantageusement, avant association avec l'autre plaque de verre 18 pour bombage, ces bandes sérigraphiées sur la plaque 15 sont recuites.Advantageously, before association with the
Dans la mesure où le vitrage réalisé est du type montré sur la figure 1, c'est-à-dire avec une seule plaque de verre 11 revêtue ITO en association avec une feuille de matière d'indice supérieur à celui de l'air et aussi voisin que possible de celui de l'ITO, par exemple en PU, les bandes conductrices 14a et 14b sont elles aussi soit sérigraphiées soit en clinquants. Elles sont alors en contact avec la couche ITO.Insofar as the glazing produced is of the type shown in FIG. 1, that is to say with a
Dans la mesure où il s'agit de bandes conductrices sérigraphiées, celles-ci peuvent être masquées de l'extérieur par un dépôt d'émail opaque non représenté sur la figure, de préférence continu tout à fait à la périphérie du vitrage, puis dégradé en pointillés du côté du centre du vitrage, la bande conductrice à l'Ag sérigraphiée étant avantageusement déposée en limite de l'émail, à cheval sur les pointillés dudit émail et sur la couche ITO seule.Insofar as they are screen-printed conductive strips, these can be masked from the outside by an opaque deposit of enamel not shown in the figure, preferably continuous entirely at the periphery of the glazing, then degraded dotted on the side of the center of the glazing, the screen-printed Ag conductive strip being advantageously deposited at the edge of the enamel, straddling the dotted lines of said enamel and on the ITO layer alone.
Avantageusement pour ce vitrage du type de celui montré sur la figure 1, les clinquants métalliques ou les bandes sérigraphiées sont masqués par un cadre en matière thermoplastique monté in situ par la technique dite d'encapsulation. Ce cadre d'encapsulation peut aussi servir de cache, de protection et d'isolant pour le brin de clinquant métallique cheminant jusqu'à sa sortie du vitrage de l'autre côté de la feuille de PU, c'est-à-dire non en contact avec la couche ITO.Advantageously, for this glazing of the type shown in FIG. 1, the metal foils or the screen-printed strips are masked by a frame of thermoplastic material mounted in situ by the technique known as encapsulation. This encapsulation frame can also serve as a cover, protection and insulation for the strand of metallic foil traveling up to its exit from the glazing on the other side of the PU sheet, that is to say not in contact with the ITO layer.
Bien entendu, une telle encapsulation est particulièrement intéressante dans le cas d'un vitrage selon la figure 3, mais elle peut également être mise en oeuvre sur un autre vitrage, par exemple celui montré figures 2 ou 3.Of course, such encapsulation is particularly advantageous in the case of a glazing according to FIG. 3, but it can also be implemented on another glazing, for example that shown in FIGS. 2 or 3.
Ainsi donc, les bonnes propriétés de la couche ITO permettent son association avec des verres teintés dans leur masse. Il en résulte un vitrage à propriétés électriques, optiques et thermiques intéressantes.Therefore, the good properties of the ITO layer allow its association with mass-tinted glasses. The result is glazing with interesting electrical, optical and thermal properties.
Des épaisseurs de plaques de verre ont été proposées précédemment grâce auxquelles les réglementations sont respectées, mais bein entendu des épaisseurs plus faibles que celles proposées sont à fortiori acceptables, le coefficient TL n'en sera que plus élevé.Thicknesses of glass plates have been proposed previously, by virtue of which the regulations are respected, but, of course, thinner thicknesses than those proposed are a fortiori acceptable, the coefficient T L will only be higher.
La solidité de cette couche autorise le bombage de son support après dépôt, sans précaution particulière même lorsqu'après bombage ladite couche est disposée sur la face convexe de son support.The solidity of this layer allows the bending of its support after deposition, without special precautions even when after bending said layer is arranged on the convex face of its support.
Ce viltrage peut être utilisé en tant que pare-brise chauffant pour automobile.This filtering can be used as a heated windshield for cars.
Claims (8)
- Glazing comprising at least one soda-lime-silica glass sheet, coloured in the mass and with reduced energy transmission, characterized in that said sheet is formed from a glass containing colouring oxides in the following approximate weight proportions:Fe2O3 : 0.55 to 0.62%FeO : 0.11 to 0.16%CoO : less than 12 ppm.
- Glazing according to claim 1, characterized in that the Fe2+/Fe ratio in the glass forming the sheet is approximately 0.19 to 0.25.
- Glazing according to either of the preceding claims, characterized in that the glass sheet has a light transmission to energy transmission ratio TL/TE of approximately 1.30.
- Glazing according to any one of the preceding claims, characterized in that the glass sheet has a TL of approximately 78% and a TE of approximately 60%, more specifically for a thickness of approximately 3.85 nm.
- Glazing comprising at least one soda-lime-silica glass sheet, coloured in the mass and with a reduced energy transmission, characterized in that said sheet is formed from a glass containing colouring oxides in the following approximate weight proportions:Fe2O3 : 0.75 to 0.90%FeO : 0.15 to 0.22%CoO : less than 17 ppm.
- Glazing according to claim 5, characterized in that the Fe2+/Fe ratio in the glass forming the sheet is approximately 0.20.
- Glazing according to claim 5 or 6, characterized in that the glass sheet has a light transmission to energy transmission ratio TL/TE of approximately 1.40 or 1.50.
- Glazing according to one of the preceding claims, characterized in that the thickness of the sheet can be 3.5 or 4 mm and that it is coloured green.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8810138A FR2634753B1 (en) | 1988-07-27 | 1988-07-27 | GLAZING WITH ELECTRICALLY CONDUCTIVE LAYER OBTAINED BY PYROLYSIS OF POWDERED COMPOUNDS, USEFUL AS A WINDSCREEN FOR A MOTOR VEHICLE |
FR8810138 | 1988-07-27 | ||
EP89402097A EP0353140B1 (en) | 1988-07-27 | 1989-07-25 | Process to produce a curved glass |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP89402097.3 Division | 1989-07-25 |
Publications (3)
Publication Number | Publication Date |
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EP0616883A2 EP0616883A2 (en) | 1994-09-28 |
EP0616883A3 EP0616883A3 (en) | 1994-11-30 |
EP0616883B1 true EP0616883B1 (en) | 1997-09-17 |
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Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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EP94109000A Revoked EP0616883B1 (en) | 1988-07-27 | 1989-07-25 | Electriacally conductive glass pane obtained by pyrolysis of powder compounds for use as a windscreen for a vehicle |
EP89402097A Expired - Lifetime EP0353140B1 (en) | 1988-07-27 | 1989-07-25 | Process to produce a curved glass |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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EP89402097A Expired - Lifetime EP0353140B1 (en) | 1988-07-27 | 1989-07-25 | Process to produce a curved glass |
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US (2) | US5786289A (en) |
EP (2) | EP0616883B1 (en) |
JP (1) | JP2788294B2 (en) |
KR (1) | KR970007318B1 (en) |
AT (2) | ATE158229T1 (en) |
BR (1) | BR8903659A (en) |
CA (1) | CA1340654C (en) |
DE (2) | DE68921519T2 (en) |
ES (2) | ES2072310T3 (en) |
FI (1) | FI102257B (en) |
FR (1) | FR2634753B1 (en) |
PT (1) | PT91284B (en) |
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US5593929A (en) * | 1990-07-30 | 1997-01-14 | Ppg Industries, Inc. | Ultraviolet absorbing green tinted glass |
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-
1989
- 1989-07-24 BR BR898903659A patent/BR8903659A/en not_active IP Right Cessation
- 1989-07-25 AT AT94109000T patent/ATE158229T1/en not_active IP Right Cessation
- 1989-07-25 AT AT89402097T patent/ATE119471T1/en not_active IP Right Cessation
- 1989-07-25 ES ES89402097T patent/ES2072310T3/en not_active Expired - Lifetime
- 1989-07-25 DE DE68921519T patent/DE68921519T2/en not_active Expired - Fee Related
- 1989-07-25 ES ES94109000T patent/ES2109550T3/en not_active Expired - Lifetime
- 1989-07-25 DE DE68928329T patent/DE68928329T2/en not_active Expired - Fee Related
- 1989-07-25 EP EP94109000A patent/EP0616883B1/en not_active Revoked
- 1989-07-25 EP EP89402097A patent/EP0353140B1/en not_active Expired - Lifetime
- 1989-07-26 PT PT91284A patent/PT91284B/en not_active IP Right Cessation
- 1989-07-26 JP JP1191574A patent/JP2788294B2/en not_active Expired - Lifetime
- 1989-07-26 FI FI893581A patent/FI102257B/en not_active IP Right Cessation
- 1989-07-27 CA CA000606816A patent/CA1340654C/en not_active Expired - Fee Related
- 1989-07-27 KR KR1019890010619A patent/KR970007318B1/en not_active IP Right Cessation
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1994
- 1994-01-07 US US08/178,655 patent/US5786289A/en not_active Expired - Fee Related
- 1994-05-09 US US08/239,929 patent/US5418025A/en not_active Expired - Fee Related
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ES2072310T3 (en) | 1995-07-16 |
DE68928329T2 (en) | 1998-04-09 |
FR2634753A1 (en) | 1990-02-02 |
DE68928329D1 (en) | 1997-10-23 |
ATE119471T1 (en) | 1995-03-15 |
EP0616883A2 (en) | 1994-09-28 |
US5418025A (en) | 1995-05-23 |
PT91284A (en) | 1990-02-08 |
FI102257B1 (en) | 1998-11-13 |
FI893581A0 (en) | 1989-07-26 |
DE68921519D1 (en) | 1995-04-13 |
DE68921519T2 (en) | 1995-11-09 |
FI893581A (en) | 1990-01-28 |
FI102257B (en) | 1998-11-13 |
JPH0280353A (en) | 1990-03-20 |
ES2109550T3 (en) | 1998-01-16 |
EP0616883A3 (en) | 1994-11-30 |
EP0353140B1 (en) | 1995-03-08 |
US5786289A (en) | 1998-07-28 |
BR8903659A (en) | 1990-03-13 |
KR900001613A (en) | 1990-02-27 |
EP0353140A1 (en) | 1990-01-31 |
KR970007318B1 (en) | 1997-05-07 |
FR2634753B1 (en) | 1992-08-21 |
CA1340654C (en) | 1999-07-13 |
ATE158229T1 (en) | 1997-10-15 |
JP2788294B2 (en) | 1998-08-20 |
PT91284B (en) | 1995-03-01 |
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